CHAPTER 1

INTRODUCTION

1.1 Biodiesel Importance

The declining reserves of fossil fuels and the growing environmental concerns
have made renewable energy an exceptionally attractive alternative energy
source for the future [1, 2]. Biodiesel is one of these promising alternative
resources for diesel engines. It is defined as the mono-alkyl esters of long chain
fatty acids derived from vegetable oils or animal fats and alcohol with or without
a catalyst. It is renewable, biodegradable, environmentally friendly, non-toxic,
portable, readily available and eco- friendly fuel [3–6]. There are different
potential feed stocks for biodiesel production. The use of edible vegetable oils
or the first generation feed stocks has been of great concern recently; this is
because they raise many concerns such as food versus fuel debate that might
cause starvation especially in the developing countries and other environmental
problems caused by utilizing much of the available arable land. This problem
can create serious ecological imbalances as countries around the world began
cutting down forests for plantation purposes. Hence, use of these feed stocks
could cause deforestation and damage to the wildlife. Therefore, non-edible
vegetable oils or the second generation feedstock have become more attractive
for biodiesel production. These feed stocks are very promising for the
sustainable production of biodiesel. Some examples of non-edible oilseed crops
are Jatropha curcas, Calophyllum inophyllum , Sterculia feotida, waste cooking
oil, castor seed oil.

1.2 Potential of Castor Seed Oil as a Feedstock for Biodiesel production

The castor oil is a colorless or pale yellowish liquid extracted from the seeds of
the castor-oil plant. Castor (Ricinus communis L) is cultivated around the world
because of the commercial importance of its oil which is used in the
manufacture of a number of industrial chemicals like surfactants, greases and
lubricants (Hailegiorgis et al. 2016). Some reports presented in the literature

1
(Sánchez, Encinar, et al. 2015),(Kilic et al. 2013),(Sánchez et al. 2015), (Dias et
al. 2013) have showed conditions for biodiesel production by trans esterification
of castor oil with methanol. However the high cost of this oil, coupled with high
viscosity, has greatly led to its industrial application (Nurdin et al. 2015), (Amin
et al. 2016). Castor oil belongs to the group considered strategic raw materials
for the production of biodiesel (Verma et al. 2016), especially because it has a
low acid value, iodine and saponification index(Amin et al. 2016). The yield
reported is near to 90% (Kilic et al. 2013), (Dias et al. 2013), so the productive
process is attractive. However, biodiesel from Castor oil shows higher viscosity
than the proposed specification, so it can be sometimes considered not suitable
(Santana et al. 2010). Additionally, the cost of Castor oil is higher than other
oils. In this way it is possible to use blends with other oils, such as waste
cooking oil, to reduce the cost of production and the viscosity of the raw
material.

1.3 Potential of Waste Cooking Oil as a Feedstock for Biodiesel

production

On the other hand, waste cooking oil is a liquid residue originated from using
domestic and industrial oils (Ordoñez et al. 2013). Cooking oil essentially is
composed of 45% monounsaturated compounds, 12% polyunsaturated
compounds and 43% saturated compounds (Yakushin et al. 2013); however,
Chhetri et al (2008) reported that about 60% of the acids that constitute used
cooking oil are unsaturated acids. This oil can be collected and re-used
primarily to produce biodiesel (Talebian-kiakalaieh et al. 2013). Waste cooking
oil is produced principally in household, hotels and restaurants. In general, oil is
normally exposed to high temperature, humidity and oxygen for long periods of
time (Martínez-Pineda et al. 2011), in the range of 150°C to 180°C (Chhetri et
al. 2008). When oil is used for frying, reactions such as oxidation,
polymerization, hydrolysis, cyclization and isomerization typically occur
(Martínez-Pineda et al. 2011). Hydrolysis results in the release of free fatty
acids, which limit the potential use in the production of biodiesel when alkaline

2
catalysts are used (Ordoñez et al. 2013). The fatty acid profile changes during
frying, the levels of palmitic acid increased while those of linoleic acid
decreased, and high correlations were found between palmitic, oleic andlinoleic
acid in all oils (Martínez-Pineda et al. 2011).The use of waste cooking oil as
biodiesel feedstock reduces the cost of biodiesel production since the feedstock
costs constitute approximately 70-95% of the overall cost of biodiesel
production (Apostolakou et al. 2009). Hence, the use of waste cooking oils and
nonedible Oils should be given higher priority over the edible oils as biodiesel
feedstock Meng et al (2008) have reported a conversion of 89.8%; Phan and
Phan(2008) have reported a conversion of 88-90% for production of biodiesel
from waste cooking oil. Previously in our researching group (López et al. 2015),
we have obtained biodiesel from waste cooking oil with a 98% of yield and
methyl-esters percentage of 99.1%. Therefore waste cooking oil is a good
alternative for the biodiesel production (Apostolakou et al. 2009).

1.4 Ultrasound Techniques

Ultrasonic waves are energy application of sound waves which is vibrated more
than 20,000 per second. In another words, it can be defined as the sound
waves beyond human hearing limit. Human hear cannot hear sound waves with
more high-pitched sound waves of an average of 10-12 kHz. Ultrasonic or
ultrasound signals are in the order of 20 kHz- 100 kHz and above the limit of
human hearing. Ultrasonic waves were used as the first for medical research
and detectors in the 1930s and 1940s (Newman& Rozycki, 1998). Idea of the
use of ultrasound, especially in the industry since the 1980s began to develop
rapidly, and today a wide range of applications using ultrasonic waves
appeared. At present, ultrasonic waves are used in areas such as Atomization:
Water sprays for dust suppression and humidifiers, low velocity spray coating,
spray drying nozzle.

Ultrasonic irradiation has three effects. First one is rapid movement of fluids
caused by a variation of sonic pressure. It causes solvent compression and
rarefaction cycles (Mason, 1999). The second and the most important one is

3
cavitation. If a large negative pressure gradient is applied to the liquid, the liquid
will break down and cavities (cavitation bubbles) will be created. At high
ultrasonic intensities, a small cavity may grow rapidly through inertial effects.
So, bubbles grow and collapse violently. The formation and collapse of micro
bubbles are responsible for most of the significant chemical effects (Kumar et
al., 2010a). Cavitation is considered as a major factor which influences on
reaction speed. Cavity collapse increases mass transfer by disrupting the
interfacial boundary layers known as the liquid jet effect. The last effect of
ultrasound is acoustic streaming mixing.
Ultrasound has been used to accelerate the rates of numerous chemical
reactions, and the rate enhancements, mediated by cavitations , are believed to
be originated from the build-up of high local pressures (up to 1000 atm) and
temperatures (up to 5000 K), as well as increased catalytic surface areas and
improve mass transfer (Yu et al., 2010). Low frequency ultrasonic irradiation is
widely used for biodiesel production in recent years. In trans esterification
reaction, mixing is important factor for increasing biodiesel yield. Oil and
methanol are not miscible completely in biodiesel processing. Ultrasonic mixing
is an effective mixing method to achieve a better mixing and enchancing liquid–
liquid mass transfer (Ji et al., 2006). Vigorous mixing increases the contact area
between oil and alcohol phases with producing smaller droplets than
conventional stirring (Mikkola & Salmi, 2001; Stavarache et al., 2006).
Cavitation effects increase mass and heat transfer in the medium and hence
increase the reaction rate and yields (Adewuyi, 2001). Ultrasonic cavitation also
provides the necessary activation energy for initiating trans esterification
reaction. Ultrasonic waves are produced with the power converter (transducer).
Sound waves are converted to ultrasonic waves vibrating at high frequency with
quartz crystal oscillator. If ultrasound waves are used in chemical reactions and
processes it is called as sonochemistry.

4
Advantages of Ultrasound

Previous research has indicated that the ultrasonication provides the

mechanical energy for mixing and the required energy for initiating the
transesterification reaction . Low frequency ultrasonic irradiation is a useful tool
for emulsification of immiscible liquids The collapse of the cavitation bubbles
disrupts the phase boundary and causes emulsification by ultrasonic jets that
impinge one liquid to another

General comparison of ultrasound irradiation with conventional stirring:

Ultrasonic assisted trans esterification of oil presents some advantages

compared to conventional stirring methods such as; reducing reaction time,
increase the chemical reaction speed and decrease molar ratio and methanol,
increase yield and conversion. Ultrasound irradiation reduce the reaction time
compared to conventional stirring operation (Stavarache et al., 2005; Ji et al.,
2006; Hanh, et al., 2008; Mootabadi, et al., 2010; Hingu et al., 2010; Lee et al.,
2011). Stavarache et al. (2005) studied transesterification of vegetable oil with
short-chain alcohols, in the presence of NaOH, by means of low frequency
ultrasound (28 and 40 kHz). By using ultrasounds the reaction time was found
much shorter (10–40 min) than for mechanical stirring. The optimal conditions
for triolein methanolysis was methanol/triolein molar ratio of 6/1, KOH
concentration of 1 wt% and irradiation time of 30 min. But the optimal conditions
for the conventional stirring method were found to be as were methanol/triolein
molar ratio of 6/1, KOH concentration of 1 wt% and 4 h (Hanh et al.., 2008). In
transesterification of waste cooking oil with methanol 89.5% conversion was
obtained in 40 minutes whereas conventional stirring resulted in 57.5%
conversion (Hingu et al., 2010). Ultrasonic irradiation method enabled to reduce
the reaction time by 30 min or more comparing to conventional heating method
in production of biodiesel from various oils. Also this method improved
conversion rate (Hanh et al., 2007; Lee et al., 2011). In transesterification
reaction, mixing is important factor for increasing biodiesel yield. Ultrasonic

5
effect induces an effective emulsification and mass transfer compared to
conventional stirring thus reaction rate increase (Hanh et al., 2009; Hingu et al.,
2010). Ultrasound assisted method has a similar effect as microwave assisted
method that both of them reduce the separation time from 5 to 10 hours to less
than 60 minutes compared to conventional transesterification method (Kumar et
al., 2010). Also, during production of biodiesel via acid or base catalyst,
ultrasound irradiation provides a fast and easy route (Yu et al., 2010) and the
purity of glycerin increases.

The production of biodiesel from non-edible vegetable oil and waste cooking oil
using ultrasonication allows under ambient operating conditions (Kumar et al.,
2010a; Hingu et al., 2010). The transesterification reaction with methanol is
usually performed at 60°C with classical stirring. Room temperature is hardly
competitive in terms of energy consumption. Room temperature is hardly
competitive in terms of energy consumption. The production of biodiesel with
ultrasound is effective and time and energy saving and economically functional
method (Ji et al., 2006; Kumar et al., 2010a; Hanh et al., 2011). Power
ultrasonic method required approximately a half of the energy that was
consumed by the mechanical stirring method (Ji et al., 2006). Special mixing
devices can be used to increase mass transfer. It was reported that
sonochemical reactors consume only about one third the energy required for a
specialty mixer for same conversion (Lifka & Ondruschka, 2004). All these
results clearly indicate that ultrasonic method inexpensive, simple and efficient
and would be promising to the conventional stirring method.

6
Chapter 2.Literature review

The objective of this project is proving the use of blends of waste cooking oil
and castor oil for biodiesel production, which is expected to reduce production
costs of biodiesel. In other way, the blend is an advantage because it reduces
the free fatty acid of the blend compared to waste cooking oil. Since the price of
waste cooking oil is about 2-3 times cheaper than virgin oils, it is an attractive
option for biodiesel production when it is mixed with castor oil.
This is a good alternative to improve the waste cooking oil which is a water
contaminant and a health problem in many countries.
Stravarache et al., (2005) studied effects of alcohol type on transesterification of
neat vegetable oil under ultrasonic and mechanical stirring. The results of
transesterfication with primary, secondary and tertiary alcohols after 60 min of
reaction were presented in Table 2.1.

N- chain alcohols (methanol, ethanol, n- propanol, and n-butanol) showed the

high yields between 88-98% in 10-20 min reaction time. The yields of biodiesel
in ultrasound activation were higher than mechanical stirring since ultrasound
produce less soap. By using ultrasound the reaction time was found much
shorter than mechanical stirring. The secondary alcohols showed some
conversion while transesterification reaction took place under stirring. Tertiary-
butanol had no conversion with both type of procedure. Hanh et al., (2009b)
produced biodiesel with triolein and various alcohols (methanol, ethanol,
propanol, butanol, hexanol, octanol and decanol). The productions were
performed at molar ratio 8:1 (alcohol: triolein) and 25°C in the presence of base
catalysts (NaOH and KOH) under ultrasonic irradiation (20 kHz) and
mechanical stirring (600 rev/min) conditions. The rate of ester formation
depended on alcohol types; as the alcohol carbon number increased, reaction
rate decreased. The secondary alcohols such as 2-propanol, 2-butanol, 2-
hexanol, and 2-octanol showed 3% conversion, suggesting that the steric
hindrance strongly affected the transesterification of triolein. N-propanol showed

7
approximately 93% conversion under ultrasonic irradiation, while 75%
conversion was obtained under mechanical stirring

Table 2.1 The studies for biodiesel production from various feed stocks at
different conditions under ultrasound irradiation.

Raw Catalyst Type of Reactor Reaction Performa Ref.

material and its alcohol& conditions time and its nce
amount Alcohol/oil temperature
molar ratio
Canola KOH Methanol & 20 kHz, 25 C& 50 >95 Thanh et
0.7wt % 5:1 1000 W min (conversi al.,
on) 2010a
Palm KOH Methanol & 45 kHz,600 38–40 C 95 % Stavarache
6:1 W 20 min (yield) et
al., 2007b
Waste KOH Methanol 20 kHz, 20-25 C 81 (yield ) Thanh et
cooking 0.7 wt % 2.5:1 (mol) 1000W 10 min 99 (yield) al.,
oil 0.3 wt % 1.5:1 (For each 20 min 2010b
step)
Coconut KOH Ethanol & 24kHz, 200 7 min >92 Kumar et
0.75 6:1 W %(yield) a2010a
wt %
Soybean NaOH Methanol & 197 kHz, 45 C 10 min 99 (yield) Ji et al.,
1wt % 6:1 150W 2006
Refined KOH 1.5 Methanol & 20 kHz, 40 C 15 min >99.4 Colucci et
soybean wt % 6:1 14.49 W (conversi al.,
oil on) 2005
Triolein NaOH Methanol 40 kHz, 25 C 25 min >95 Hanh et
KOH Ethanol & 1200 W Ultrasonic (conversi al.,
1wt % 6:1 cleaner on) 2009b
Beef KOH Methanol & 40 kHz, 60 C 70 s >92 Teixeira et

8
Tallow 0.5 wt 6:1 1200 W (conversi al.,2009
% on)
Waste KOH Methanol & 20 kHz, 45 C 40 min 89 Hingu et
cooking 1wt % 6:1 200 W (conversi al.2010
oil on)

Table 2.2 The studies for biodiesel production from various feed stocks at
different conditions under Mechanical stirring

Raw Catalys Type of Reaction time Perform Ref.

material t and alcohol& and its ance
its Alcohol/oil temperature
amount molar ratio
Karanja NaOH methanol Room temp. 89.5 Y C sharma
oil (0.5 wt 8:1 ratio yield B sing 2007
%)
Palm oil KOH methanol ( 60 C and 1 hr 93 % Abdullah
(0.5- 6:1) and 300 rpm yield volume 6,2017
2.5 wt
%)
soya KOH Methanol 350 rpm and - A S peiter 2018
bean 1.5 wt (10:1 ) 30 min
%
Castor KOH Methanol 90 min 97 % Sachin volume
oil and 1 wt % ( 6:1) 3 2017
cotton
seed oil
cooking KOH Methanol( 60 C and 1 hr 97% Athulya james
oil 1 wt % 6.25 :1) salman khan
volume 6 May
2017

9
Chapter 3.Blend Preparation

3.1 Extraction of Oil From Castor Seeds

The castor seeds were collected from the lands located in the city of
Rajkot,Gujarat. The castor seeds were cleaned and oven-dried at 50 °C for 24 h
to be ground later by an electrical grinder. The oil was extracted by n-hexane in
a Soxhlet extractor for 10 h, followed by distillation under vacuum using a rotary
evaporator to separate the oil from the solvent

Condenser

Thimble

Hexane

Hot plate Switch (ON/OFF)

Temperature Controller

Speed Controller

. Figure 3.1 set up of soxhlet extractor of castor oil

10
3.2 WCO Collection and Filtration

Waste cooking oil collected from various Restaurants and hotels near
Gandhinagar area. Remove impurities in the waste cooking oil, which would
interfere during the reaction and become particulate matter for the obtained
biodiesel. Waste cooking oil was filtered using filter paper (Whatman 1). The
filtered oil was stored in plastic containers at room temperature, until use
according to the experimental design.

3.3 Blend Preparation

The CSO and WCO were mixed and utilized in BD production. Different blends
of CSO and WCO (10, 20, 30, 40 and 50% CSO:WCO ) were prepared through
mixing CSO with WCO using a mechanical stirrer for 30 min to obtain
homogeneous mixture.

Figure 3.2 Blend Preparation through mechanical stirrer

11
3.4 Analysis

The characterization of the castor oils, waste cooking oils and blends of both
using gas chromatography equipped with Flame Ionization Detector . Acid value
and Free fatty acid values were titrated using Metrohm potentiometric titrator.
Density was measured using 10ml density bottle. Viscosity was measured using
Brookfield viscometer (LV ).

The density of castor oil obtained experimentally in this work is 0.950 g / ml,
which is within the range reported in the literature (0.9625 g / ml and 0.9772 g /
ml)(Sánchez et al. 2015). The waste cooking oil has reported density of 0.910 g
/ ml and 0.9156 g / ml(Lopez et al. 2015), comparing these with the density
values obtained in this work, we concluded that there is not a considerable
difference with values reported in the literature. Regarding the absolute
viscosity, it was determined at a temperature of 40 ° C for the two oils. Sanchez
et al (2015a) reported a value of 174.71 cP viscosity for castor oil, but the
author establishes that this value may vary depending on the source of oil
extraction.We obtained value of 195 cP. As waste cooking oil, Lopez (2015)
reported for the wasted cooking oil a value of 40 cP, close to the value obtained
in this work.

Table 3.1 Properties of Different blends

Blends of WCO + CSO Density(kg/m3) kinetic viscosity(mm2/s) at 40

C
10 ml WCO + 90 ml CSO 940.6 185.4
20 ml WCO + 80 ml CSO 931.2 150.5
30 ml WCO + 70 ml CSO 921.8 120.3
40 ml WCO + 60 ml CSO 921.4 113
50 ml WCO + 50 ml CSO 903 103.82
60 ml WCO + 40 ml CSO 893.6 90.67
70 ml WCO + 30 ml CSO 884.2 78.52
80 ml WCO + 20 ml CSO 874.2 68.31

12
90 ml WCO + 10 ml CSO 865.4 62.66

As shown in table density and kinematic viscosity of the CSO has been
significantly increase with WCO content in prepared blends

It can be seen from Table 3.2 that the fatty acid composition of the raw oils has
been markedly altered after blending. The ricinoleic acid content of the CSO
has reduced from 83.84 % to 6.76% after blending with WCO. On the other
hand, contents of palmitic and stearic acids of WCO have also changed after
blending with the CSO. These achievements could be ascribed to a possible
chemical reaction between hydroxyl groups of the ricinloeic acid and the free
fatty acids of WCO and

Table 3.2 fatty acids profile of WCO, CSO and WCO+CSO

Fatty acid composition WCO CSO 50 ml WCO + 50 ml CSO

Ricinoleic acid - 83.84 6.76
Linoleic acid 40.88 6.08 32
oleic acid 24.69 5.17 24
palmitic acid 28.65 2.09 20
stearic acid 2.49 2.09 17

or due to the dilution effect. This could also be the reason behind the reduction
in the values of CSO properties after blending with WCO

13
Table 3.3 WCO, CSO and Different WCO ml + CSO ml samples Acid value and
% FFA

Blend of WCO +CSO Acid value % FFA

WCO 1.12 0.563
10 ml WCO + 90 ml 1.05 0.528
CSO
20 ml WCO + 80 ml 1.01 0.508
CSO
30 ml WCO + 70 ml 0.97 0.488
CSO
40 ml WCO + 60 ml 0.9 0.453
CSO
50 ml WCO + 50 ml 0.87 0.437
CSO
60 ml WCO + 40 ml 0.8 0.402
CSO
70 ml WCO + 30 ml 0.75 0.377
CSO
80 ml WCO + 20 ml 0.687 0.345
CSO
90 ml WCO + 10 ml 0.59 0.297
CSO
CSO 0.568 0.285

14
Chapter 4

Mechanical stirrer assisted process for Bio diesel

Production
Materials Used: KOH pellets [Assay (KOH) > 84 %, carbonate < 2 %] ,
Methanol[Assay (KOH) Min 99.8 %, ethyl acetate[ Assay (KOH) > 84 %] fisher
chemicals.

4.1 Mechanical stirrer method and transesterification reaction

Transesterification is an equilibrium reaction and the transformation occurs

essentially by mixing the reactants. However, the presence of a catalyst
accelerates considerably the adjustment of the equilibrium [2]. Methanolysis
with 1% wt. potassium hydroxide catalyst resulted in successful conversion
giving the best yields and viscosities of the esters [3].

The stoichiometric reaction requires 1 mol of a triglyceride and 3 mol of the

alcohol. However, an excess of the alcohol is used to increase the yields of the
alkyl esters and to allow its phase separation from the glycerol formed [4]. The
optimum methanol/oil molar ratio was found to be 6:1 [3].
While transesterification is well-established, and becoming increasingly
important, there remains considerable inefficiencies in existing
transesterification processes. In conventional heating of transesterification
process (batch, continuous, and super critical methanol process), heat energy
is transferred to the raw material through convection, conduction, and radiation
from surfaces of the raw material. Thus, the conventional heating consumes
more energy and take long preheat and reaction time, optimally 1 hour [3], to
produce over 95 percent conversion yield biodiesel product.
Since this reaction can only occur in the interfacial region between the liquids
and also due to the fact that fats and alcohols are not totally miscible
transesterification is a relatively slow process. As a result, a vigorous mixing is

15
required to increase the area of contact between the two immiscible phases,
and thus to produce an emulsion.
4.2 Description of mechanical stirrer method

The purpose of mixing methanol and the catalyst (KOH) is to react the two
substances to form Methoxide. The amount of Methanol used 99% pure with
molar ratio (6:1 to 9:1) and KOH (0.5-1%) of the volume of the oil.

Mechanical stirring machine consist of temperature controller to control

temperature within the range of 0-100º C and speed controller is for controlling
speed of stirrer in terms of revolution per minute (rpm). In this machine hot plate
functions as a heating source to maintain the temperature of the solution. The
beaker is placed on the hot plate then vegetable oil as per the requirement was
poured into it at the beginning. The reaction started when a quantities amount
of methanol liquor dissolved in catalyst was poured into the beaker and then
immediately drops the magnetic stirrer so that through its stirring action at a
particular rpm, dilution of mixture can take place by switching the button on. The
Trans esterification reaction was carried by conventional mechanical stirring
process, photograph is shown in figure.4.1

16
 Condenser

Mixture of
Methanol+oil Hot plate

Switch (ON/OFF)
Speed Controller
Temperature Controller

Figure 4.1 set up of Mechanical stirrer

Tranesterification also called alcoholysis is the displacement of alcohol from an

ester by another alcohol in a process similar to hydrolysis except that an alcohol
is used instead of water. This has been widely used to reduce the viscosity of
the triglycerides.

Figure 4.2 Transesterification reaction

17
Chapter 5.

Ultrasound assisted process for Bio diesel Production

Ultrasonic cleaning bath, ultrasonic probe which are usually operated at a fixed
frequency are mainly used as ultrasonic apparatus. Frequency is dependent on
particular type of transducer which is 20 kHz for probes and 40 kHz for bath.
Ultrasonic processing of biodiesel involves the following steps: 1. Mixing oil with
the alcohol (methanol) and catalyst, 2. Heating the mixture, 3. The heated
mixture is being sonicated inline, 4. Glycerin separation by using centrifuge.
The factors affecting ultrasound assisted biodiesel production are: Effect of
catalyst type on ultrasound assisted biodiesel production, Effect of alcohol type
on ultrasound assisted biodiesel production, Effect of ultrasonic power on
biodiesel processing, Frequency effect on ultrasonic assisted biodiesel
production. Effect of catalyst type on ultrasound assisted biodiesel production:
In ultrasonic assisted biodiesel studies homogen (alkaline, acid), heterogen and
enzyme catalyst were studied oil under ultrasonic irradiation. Trans
esterification reactions have been studied with KOH catalyst blended oil
(Stavarache et al., 2007a; Lee et al., 2011), waste cooking oil (Thanh et al.,
2010b; Hingu et al.,2010). KOH and NaOH were used for ultrasound assisted
transesterification of neat vegetable oil. They used 1% alkali catalyst amount,
6:1 molar ratio methanol to oil and room temperature.) As it is known,
ultrasound increase mixing of oil and alcohol with catalyst phases, as well as
increase catalytic surface area. Catalyst can be broken into smaller particles by
ultrasonic irradiation to create new sites of the subsequent reaction. Thus, solid
catalyst is expected to last longer in the ultrasonic-assisted process (Mootabadi
et al., 2010).

High acidity oils can be transesterified by two-step processes. In the first step,
free fatty acids are converted to esters by direct esterification with acid catalyst.
Eq. 1 shows esterification of fatty acids. In the second step, basic catalyst was
used to esterify triglycerides.

18
 RCOOH +CH3OH →RCOOCH3 + H2O (1)

Probe

Water bath

Stand Table

Figure 5.1 ultrasound machine

19
Chapter 6 Results and Discussion

Gas chromatography analysis

Equipment Details

1. Gas Chromatography occupied with Mass Spectrometry from Agilent

Technologies India Pvt. Ltd
2. GC model - 7890A and MS model – 5975C
3. GCMS fitted with Thermal conductivity detector (TCD) and Flame
Ionization detector(FID) along with capillary column HP- 5MS
(50m×0.25mm×0.25µm)
4. Nitrogen as carrier gas with 99.99% purity
5. General Procedure for GC-FID
 First start GCMS and wait for tuning & stabilization.
 Setup the method along with oven temperature, detector temperature,
injector temperature, ramp, inject quantity, post run time, hold time

For doing GC analysis, sample preparation was done by diluting 2%bidiesel in 3

ml of ethyl acetate. From this 1ml sample was injected in GC. The program set
for GC was injector temperature 250°c and detector temperature 280°c. Oven
temperature started from 100°c hold for 1 min, then increased to 160°c at rate
of 20°c/min and held at 160°c for 5 min and finally increased to 25°c at rate of
5°c/min and held there for 9 min. Nitrogen is used as carrier gas. Results were
compared to standards available.
The results obtained for biodiesel production are presented in Table 6.1 Yield is
defined as the ratio of produced methyl esters to initial oil weight and
conversion is the ratio of converted oil weight to initial oil weight (Al-Hamamre
and Yamin 2014). According to this Table, in all trials yields above 80% were
obtained. Lopez et al (2015) reported a yield of 80%, Chuah et al(2016)
reported a yield of 97% and Phan and Phan(2008) reported a yield of 88-
90%for waste cooking oil. For castor oil, Kilic et al (2013) have reported a yield

20
upper of 90% and Dias et al(2013) a yield of 92%. These results show that the
addition of waste cooking oil to the oil mixture does not affect yield, so castor oil
may be partially replaced by waste cooking oil until 20%. Conversion is upper of
90% for all trials and it is similar to other reports presented in the consulted
literature (Meng et al. 2008), (López et al. 2015).

Table 6.1 Properties of biodiesel prepared through conventional stirring

Blends of WCO Density kinematic viscosity calorific % yield

+CSO (kg/m3) (mm2/sec) at 40 C value
(MJ/KJ)
10 ml WCO + 90 923.38 13.4 39.55 82.4
ml CSO
20 ml WCO + 80 910.29 13.6 39.95 85.2
ml CSO
30 ml WCO + 70 905.5 10.52 40.17 88.3
ml CSO
40 ml WCO + 60 902.84 8.44 40.42 91.3
ml CSO
50 ml WCO + 50 902.1043 10.93 40.71 88.38
ml CSO
60 ml WCO + 40 886.56 9.08 40.83 81.95
ml CSO
70 ml WCO + 30 895.89 6.34 41.281 83.9
ml CSO
80 ml WCO + 20 894 5 41.72 88.76
ml CSO
90 ml WCO + 10 889.28 5.6 42.46 85.44
ml CSO

21
The calorific value obtained for all samples of biodiesel are in the range of
39.55 MJ / kg to 42.46 MJ/Kg as shown in Table 6.1. In this table it is seen that
the presence of the waste cooking oil in the oil mixture makes the calorific value
increases. Biodiesel has a higher calorific power produced only from used
cooking oil, followed by 10% mixture of castor oil and 90% waste cooking oil. As
presented in the literature, the calorific value of biodiesel from castor oil is at
36,947.4 J / g (Nurdin et al. 2015),(Amin et al. 2016) and waste cooking oils in
37,520 J / g (Kathirvel et al. 2016). These results confirm that the biodiesel
obtained complies with the reports and that there is a considerable change in
the calorific value by adding waste cooking oil to castor oil.

Table 6.2 Properties of biodiesel prepared through Ultrasound technique

Blends of WCO Density ( Kinematic calorific % yield
+CSO kg/m3) viscosity value
(mm2/sec) at 40 C (MJ/KJ)
10 ml WCO + 90 916.75 8.61 39.75 91.2
ml CSO
20 ml WCO + 80 912.08 8.45 39.95 92.7
ml CSO
30 ml WCO + 70 909.45 8.32 40.37 91.4
ml CSO
40 ml WCO + 60 903.27 8.09 40.52 94.4
ml CSO
50 ml WCO + 50 901 7.65 40.71 96.9
ml CSO
60 ml WCO + 40 898.08 7.35 40.93 95.09
ml CSO
70 ml WCO + 30 895.91 6.87 41.251 96.53
ml CSO
80 ml WCO + 20 892.64 5.5 41.82 96.70
ml CSO

22
90 ml WCO + 10 890.08 5.32 42.86 93.31
ml CSO

Conclusion

Biodiesel was obtained from blends of castor oil and waste cooking oil by trans
esterification. The results obtained in this work showed that the yield, for blends
of castor oil with waste cooking oil, were up to 80%, being the mixture of 60%
castor oil and 40% waste cooking oil that obtained the greater yield (91.3%). In
addition the calorific value obtained for this mixture is 40.42MJ/kg being
evaluated and there is no greater difference with respect to the biodiesel
obtained entirely from waste cooking oil. In terms of costs it can be said that the
castor oil is above the waste cooking oil 70%, and with the blends it reduces
the cost of the biodiesel to 30% less compared to if only castor oil were used.
With this work, it can be concluded that it is possible to integrate the waste
cooking oil into productive processes to obtain biodiesel from castor oil, and
reduce the costs of the biodiesel generated. In addition, it will be possible to
integrate used cooking oil into a production process without continuing to
generate impacts on the environment.
From Table 6.1 and 6.2 we can seen that 80 % of WCO composition in CSO
and 90 % of WCO in CSO kinematics viscosity close to ASTM standard
(Kinematic viscosity is 1.9-6 mm2/sec at 40 C ). And we also claim that
ultrasound technique assisted biodiesel kinematics viscosity more close to
ASTM standard biodiesel than the conventional stirring.

23
 16

14
stirring
12
Ultrasound
10
kinematic 8
viscosity at
40 C 6

0
10 20 30 40 50 60 70 80 90
% of WCO in blends

Figure 6.1 kinematic viscosity versus % WCO in blends through Mechanical

stirring and ultrasound

From figure 6.1 we claim that kinematic viscosity increases with increases
Castor oil composition in blends .and ultrasound method give close value to
Biodiesel ASTM standard.

24
 44
stirring
43
ultrasound
42
calorific
value ( 41
MJ/KJ)
40

39

38

37
1 2 3 4 5 6 7 8 9
% of WCO in Blends

Figure 6.2 calorific value versus % WCO in blends through Mechanical stirring
and ultrasound

From figure 6.2 calorific value increases with increasing WCO composition in
Blends.and Ultrasound have slight higher value than the conventional stirring.

25
 100
stirring

ultrasound
95

90
%
yield
85

80

75

70
10 20 30 40 50 60 70 80 90

% of WCO in blends

Figure 6.3 % yields versus % WCO in blends through Mechanical stirring and
ultrasound

From Figure 6.3 we conclude that ultrasound technique have higher yield than
the conventional stirring. we obtain higher yield in 40 % WCO composition in
blends.

26
 930
stirring
920
ultrasound
910

900
Density890

880

870

860
10 20 30 40 50 60 70 80 90
% of WCO in blends

Figure 6.4 % Density versus % WCO in blends through Mechanical stirring and
ultrasound

From Figure 6.4 we can say that Biodiesel produced through Mechanical stirrer
ave higher density than the ultrasound

27
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